US20240010404A1 - Layered body for packaging - Google Patents

Layered body for packaging Download PDF

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Publication number
US20240010404A1
US20240010404A1 US18/025,516 US202118025516A US2024010404A1 US 20240010404 A1 US20240010404 A1 US 20240010404A1 US 202118025516 A US202118025516 A US 202118025516A US 2024010404 A1 US2024010404 A1 US 2024010404A1
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Prior art keywords
film
layered body
adhesive
layer
resin
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US18/025,516
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English (en)
Inventor
Seishi Yoshikawa
Koki SHIBATA
Atsushi Ebata
Kenya MAJIMA
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Toyo Seikan Group Holdings Ltd
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Toyo Seikan Group Holdings Ltd
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Assigned to TOYO SEIKAN GROUP HOLDINGS, LTD. reassignment TOYO SEIKAN GROUP HOLDINGS, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAJIMA, Kenya, SHIBATA, Koki, YOSHIKAWA, SEISHI, EBATA, ATSUSHI
Publication of US20240010404A1 publication Critical patent/US20240010404A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a layered body for packaging, and more particularly to a layered body for packaging that exhibits excellent oxygen barrier properties.
  • Resin films represented by polypropylene films and olefin resin films such as polyethylene have been widely used as packaging materials for many years because they are inexpensive and can be easily bonded by heat sealing to form a pouch.
  • forming an inorganic coating on the surface of the resin film is known as means for improving the gas barrier properties, and providing a vapor-deposited film of aluminum, silicon oxide, or the like, a coating film mainly composed of silicon oxide, a coating film formed by a crosslinking reaction between a carboxylic acid and a metal, a coating film in which a metal oxide is dispersed, or the like is known. Furthermore, providing the above-described coating film on the above-described vapor-deposited film is known. A resin film having such an inorganic coating on the surface thereof exhibits high gas barrier properties and is therefore commercially available as a barrier film.
  • a heat-sealing resin layer is usually provided. Such a heat-sealing resin layer is bonded to the barrier film using an adhesive.
  • Patent Document 1 discloses a layered body for packaging including a substrate film having the vapor-deposited film and the heat-sealing resin layer provided on the vapor-deposited film via an adhesive layer, wherein the adhesive layer is formed of a cured product of a two-part curable adhesive containing a polyester polyol, an isocyanate compound, and a phosphoric acid-modified compound.
  • the adhesive layer is provided for bonding layers formed of different materials
  • the heat-sealing resin layer is provided for joining the same kind of resin (heat-sealing resin), and is different from the adhesive layer.
  • a pouch obtained by bag making using this layered body for packaging ensures sufficient oxygen barrier properties unless retort sterilization is performed, but when retort sterilization is performed, the oxygen barrier properties are greatly decreased. Therefore, it is difficult to use such a layered body for packaging as a pouch for retort foods.
  • the decrease in oxygen barrier properties after the retort sterilization is considered to be caused by the shrinkage of the substrate film and the generation of defects in a vapor-deposited layer due to heating during the retort sterilization.
  • Such a decrease in oxygen barrier properties due to heating occurs not only when the vapor-deposited film is formed but also when other inorganic coatings are provided. Therefore, there is a need to ensure excellent oxygen barrier properties by the inorganic coating even after retort sterilization.
  • Patent Document 2 discloses a gas barrier polyolefin laminated film having a polyolefin film layer and a gas barrier layer.
  • the gas barrier layer is a film layer obtained by curing an epoxy resin containing an aromatic ring in the molecule with an epoxy resin curing agent, and exhibits excellent oxygen barrier properties.
  • the gas barrier layer does not have an inorganic coating such as a vapor-deposited film, oxygen barrier properties as high as those of a barrier film having an inorganic coating are not obtained regardless of the presence of retort sterilization.
  • an object of the present invention is to provide a layered body for packaging that exhibits excellent oxygen barrier properties even when subjected to heat treatment such as retort sterilization.
  • a layered body for packaging including a barrier film having an inorganic coating formed on a surface of a thermoplastic resin film, and an adhesive layer provided on the inorganic coating, wherein the adhesive layer is formed of an epoxy-based adhesive.
  • the following aspects are preferably applied.
  • a pouch obtained by bonding the above-described layered body for packaging by heat sealing.
  • the pouch preferably contains an olefin-based resin at a ratio of 80% by mass or more.
  • a layered body for packaging including a barrier film having an inorganic coating formed on a surface of a thermoplastic resin film in which an adhesive layer is provided on the inorganic coating, wherein the adhesive layer has a storage elastic modulus higher than 39 MPa at 120° C.
  • the layered body for packaging of the present invention has a basic structure including a barrier film having an inorganic coating and a heat-sealing resin layer, and has an important feature in that the adhesive layer provided between the barrier film (inorganic coating) and the heat-sealing resin layer is formed of an epoxy-based adhesive, whereby excellent oxygen barrier properties can be obtained even after retorting.
  • the adhesive layer formed of an epoxy-based adhesive exhibits a large storage elastic modulus at a high temperature, particularly at 120° C.
  • the adhesive layer formed between a heat-sealable film and the inorganic coating is formed of an epoxy-based adhesive
  • the storage elastic modulus thereof is as high as 57 MPa (at 120° C.)
  • the oxygen permeability before retorting is 0.05 cc/m 2 /day/atm and after retorting is 1.75 cc/m 2 /day/atm, which is slightly higher.
  • the storage elastic modulus of the adhesive layer formed of a urethane-based adhesive is 2.4 MPa (at 120° C.), which is considerably lower than that of the adhesive layer of Example 1 formed of an epoxy-based adhesive. It is understood that such a pouch obtained by forming the layered body of Comparative Example 1 not only exhibits an oxygen permeability of 1.04 cc/m 2 /day/atm before retorting, which is slightly higher than that of Example 1, but also exhibits a significantly increased oxygen permeability of 12.54 cc/m 2/day/atm after retorting.
  • the storage elastic modulus of the adhesive layer of Comparative Example 3 formed of a urethane-based adhesive of a type different from that of Comparative Example 1 is 39 MPa (at 120° C.), which is higher than that of the adhesive layer of Comparative Example 1, but still lower than that of the adhesive layer of Example 1 formed of an epoxy-based adhesive.
  • the pouch obtained from such a layered body of Comparative Example 3 shows a significant increase in oxygen permeability of 11.58 cc/m 2 /day/atm after retorting.
  • the adhesive layer formed of an epoxy-based adhesive has a large storage elastic modulus at 120° C., for example, larger than 39 MPa.
  • a layered body of a barrier film having an inorganic coating such as a vapor-deposited film and the adhesive layer has a high thermal shrinkage ratio and shrinks significantly when heated in a retort treatment.
  • the adhesive layer formed of an epoxy-based adhesive has a high storage elastic modulus at a high temperature, the thermal shrinkage of the layered body of the barrier film and the adhesive layer is considered to be suppressed, and the occurrence of cracks and pinholes in the inorganic coating due to the shrinkage is considered to be effectively suppressed.
  • the layered body for packaging of the present invention exhibits excellent oxygen barrier properties not only before retorting but also after retorting, and thus is suitably used as a pouch for retort food.
  • FIG. 1 is a schematic cross-sectional side view illustrating the basic structure of the layered body for packaging of the present invention.
  • the layered body for packaging of the present invention has a basic structure in which an adhesive layer 3 is formed on a barrier film 1 , and, for example, a heat-sealing resin layer 5 is adhered on the adhesive layer 3 .
  • the barrier film 1 has an inorganic coating 1 b formed on a thermoplastic resin film 1 a , and a heat-sealing film is bonded onto the inorganic coating 1 b of the barrier film 1 with an adhesive to form, for example, a heat-sealing resin layer 5 via the adhesive layer 3 .
  • Thermoplastic Resin Film 1 a Thermoplastic Resin Film 1 a;
  • the thermoplastic resin film 1 a serves as a base of the inorganic coating 1 b , and is produced by a known means such as extrusion or co-extrusion molding.
  • thermoplastic resins are not limited in principle, and various thermoplastic resins can be used including olefin-based resins including, for example, polyolefins such as low-density polyethylene, high-density polyethylene, medium density polyethylene, polypropylene, poly(l-butene); poly(4-methyl-1-pentene), or random or block copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and cyclic olefin copolymers.
  • polyolefins such as low-density polyethylene, high-density polyethylene, medium density polyethylene, polypropylene, poly(l-butene); poly(4-methyl-1-pentene), or random or block copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and cyclic olefin copolymers.
  • thermoplastic resin film 1 a In addition to the above-described olefin-based resins, the following resins can be used for forming the thermoplastic resin film 1 a.
  • Ethylene-vinyl compound copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl chloride copolymer;
  • Styrene-based resins such as polystyrene, acrylonitrile-styrene copolymer, ABS, and ⁇ -methylstyrene-styrene copolymer;
  • Polyvinyl-based resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, polymethylacrylate, and polymethyl methacrylate;
  • Polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, and nylon 12;
  • Thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN);
  • resins such as polycarbonate, polyphenylene oxide, polyimide resin, polyamideimide resin, polyetherimide resin, fluorine resin, allyl resin, polyurethane resin, cellulose resin, polysulfone resin, polyethersulfone resin, ketone resin, amino resin, and polylactic acid.
  • thermoplastic resin film 1 a may be a blend of the resins exemplified above, or a resin obtained by appropriately modifying any of these resins by copolymerization (for example, an acid-modified olefin-based resin).
  • the thermoplastic resin film 1 a is preferably an olefin-based resin film from the viewpoint of being used for forming retort pouches having high recyclability, and is more preferably polypropylene from the viewpoint of strength of pouches and the like.
  • thermoplastic resin film 1 a is preferably stretched in one or two axial directions from the viewpoint of having sufficient heat resistance to withstand retort sterilization.
  • the stretching ratio may be such that film breakage due to overstretching does not occur, and is usually 2 times or more.
  • thermoplastic resin film 1 a described above may have an appropriate thickness according to the capacity of the pouch to be finally manufactured or the like, but if it is excessively thin, the strength may be reduced due to loss of orientation or the like when forming the inorganic coating 1 b described later. Therefore, the thermoplastic resin film 1 a preferably has a thickness of at least 10 ⁇ m or more.
  • the inorganic coating 1 b provided on the thermoplastic resin film 1 a described above is provided to ensure oxygen barrier properties, and examples thereof include vapor-deposited films of various metals or metallic oxides, silicon-oxide-based coating films, coating films formed by crosslinking reaction between carboxylic acids and metals, and coating films in which metallic oxides are dispersed. Further, the coating film may be provided on the vapor-deposited film described above.
  • the formed film is dense and high-oxygen barrier properties can be obtained, and thus the inorganic coating 1 b is preferably a coating in which a silicon-oxide-based coating film is provided on a vapor-deposited film.
  • the vapor-deposited film is an inorganic vapor-deposited film formed by techniques such as physical vapor deposition represented by sputtering, vacuum vapor deposition, ion plating, or the like, and chemical vapor deposition typified by plasma CVD, or the like, which is a film formed of various metals or metal oxides, for example. Since such a vapor-deposited film is formed of an inorganic substance, it exhibits higher oxygen barrier properties against a gas barrier resin such as an ethylene-vinyl alcohol copolymer.
  • a gas barrier resin such as an ethylene-vinyl alcohol copolymer.
  • a vapor-deposited film formed of silicon oxide or aluminum oxide, especially silicon oxide exhibits the highest barrier properties against oxygen, and thus is most suitable.
  • the thickness of the inorganic coating 1 b described above varies depending on the level of oxygen barrier properties required, while in the case of the vapor-deposited film, the inorganic coating 1 b should be thick enough to ensure an oxygen permeability of not more than 1 cc/m 2 /day/atm without impairing the properties of the underlying thermoplastic resin film 1 a upon vapor deposition, and the thickness may be generally from about 1000 to 10 nm, particularly from about 100 to 10 nm.
  • the adhesive layer 3 is formed of an epoxy-based adhesive.
  • the adhesive layer 3 formed in this manner is a layer exhibiting adhesiveness and, at the same time, exhibiting a large storage elastic modulus as described above, where, for example, the storage elastic modulus at 120° C. is larger than 39 MPa (at 120° C.), particularly 45 MPa or more. That is, since the adhesive layer 3 formed of an epoxy-based adhesive exhibits a large storage elastic modulus at 120° C., it is possible to effectively avoid a decrease in oxygen barrier properties when a heat treatment at a temperature of from about 100 to 120° C. such as retort sterilization is performed.
  • the above-described epoxy-based adhesive is a so-called dry laminate adhesive, and is used for adhering by curing a liquid epoxy resin with an epoxy curing agent.
  • a layer such as the heat-sealing resin layer 5 is adhered and fixed on the inorganic coating 1 b by the adhesive layer 3 formed by using the epoxy-based adhesive.
  • the epoxy resin described above is a liquid resin having an epoxy group in the molecule, and typical examples thereof include those obtained by reaction of epichlorohydrin with a phenol compound, an amine compound, a carboxylic acid or the like, and those obtained by oxidation of an unsaturated compound such as butadiene with an organic peroxide or the like, and any type of epoxy resin can be used.
  • Specific examples thereof include, but are not limited to, bisphenol A type or bisphenol F type epoxy resins, novolac type epoxy resins, cyclic aliphatic type epoxy resins, long chain aliphatic type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and the like.
  • a glycidylamine type epoxy resin is particularly preferable in that an adhesive layer having a high elastic modulus can be formed.
  • epoxy curing agent a known epoxy curing agent such as an amine-based curing agent, an acid anhydride, or a polyamide can be used.
  • an amine-based curing agent particularly an aromatic polyamine typified by metaphenylene diamine is suitably used.
  • the amount ratio between the epoxy resin and the curing agent may be set so that a sufficient cured film is formed according to the epoxy equivalent weight of the epoxy resin.
  • the epoxy-based adhesive described above is applied onto the above-described inorganic coating 1 b using volatile organic solvents such as hydrocarbons, alcohols, ketones, esters, and ethers, and dried to form the adhesive layer 3 on the inorganic coating 1 b.
  • volatile organic solvents such as hydrocarbons, alcohols, ketones, esters, and ethers
  • the high storage elastic modulus at 120° C. exhibited by the adhesive layer 3 is obtained only by the epoxy-based resin at present, and the high storage elastic modulus cannot be obtained by the urethane-based adhesive.
  • even other adhesives are considered to be capable of effectively avoiding the deterioration of the oxygen barrier properties when heat treatment such as retort sterilization is performed as long as they exhibit a high storage elastic modulus at 120° C. as in the present invention.
  • the heat-sealing resin layer 5 is formed by superposing and pressure-bonding the heat-sealing film on the adhesive layer 3 described above and curing the adhesive in this state. That is, since the resin layer 5 is easily melted by heating and is immediately solidified by cooling, the layered body can be thermally adhered to various objects by using this, and a pouch can be produced by thermally adhering (heat-sealing) such layered bodies to each other.
  • curing of the adhesive is performed by holding the adhesive at a temperature of about 30 to 50° C. for 24 hours or more.
  • films formed of various thermoplastic resins can be used as the heat-sealing film used for forming the above-described heat-sealing resin layer 5 ; however, a film formed of an olefin resin is preferable in terms of cost and the like, and a CPP film (non-oriented polypropylene film, also referred to as cast PP film) is preferably used because it is necessary to ensure heat resistance and impact resistance particularly in terms of use for producing a pouch subjected to retort treatment, and a CPP film formed of impact polypropylene (impact PP) is most preferably used particularly in terms of ensuring excellent impact resistance and heat resistance.
  • a CPP film non-oriented polypropylene film, also referred to as cast PP film
  • impact PP impact polypropylene
  • the CPP film using the above-described impact PP is molded by melt extrusion of a propylene-based resin composition, and the propylene resin composition contains an impact PP component (A) and a linear low-density polyethylene (B).
  • the impact PP component (A) is formed of impact polypropylene (impact PP), and the impact PP used in the present invention has a structure in which an ethylene-propylene copolymer (EPR) is dispersed especially in a homo- or random polypropylene. That is, the dispersion of the EPR in the polypropylene imparts impact resistance to the polypropylene.
  • a known rubber component dispersed in the polypropylene includes, in addition to EPR, a styrene-butadiene copolymer (SBR), and an ethylene-propylene-butene copolymer (EPBR).
  • SBR styrene-butadiene copolymer
  • EPBR ethylene-propylene-butene copolymer
  • the impact PP as described above has a melt flow rate (MFR, 230° C.) in a range approximately from 0.5 to 10 g/10 min from a viewpoint of, for example, film formability (extrusion formability).
  • the EPR content in the above-described impact PP can be represented by a xylene soluble fraction when the CPP film used for forming the heat-sealing resin layer 5 is dissolved in boiling xylene, and the xylene soluble fraction is preferably 8% by mass or more, particularly in the range from 8 to 20% by mass. That is, when the xylene soluble fraction is smaller than the above range, the impact resistance of the pouch declines because the amount of EPR is small. On the other hand, when the soluble fraction is excessively high, the appearance of the pouch may be poor.
  • This linear low-density polyethylene is a component that functions as a compatibilizer between the polypropylene (PP) and the ethylene-propylene copolymer (EPR) when mixed with the impact PP described above and greatly improves dispersion of EPR in PP, thereby allowing EPR to sufficiently exhibit its impact improving effect.
  • Such LLDPE is a linear low-density polyethylene having a density in the range from 0.860 to 0.925 g/cm 3 , and is obtained by copolymerizing ethylene with an ⁇ -olefin such as butene-1, hexene-1,4-methylpentene-1 or octene-1, and is obtained by introducing a short-chain ⁇ -olefin chain as a branch into a long-chain ethylene chain to reduce the density, and has extremely high molecular linearity.
  • ⁇ -olefin such as butene-1, hexene-1,4-methylpentene-1 or octene-1
  • LLDPE since this LLDPE is used by being mixed with impact PP, in order to not impair film formability, LLDPE having an MFR (190° C.) from 1.0 to 15 g/10 min is suitably used, and as comonomer components, hexene-1 and 4-methylpentene-1 (methylpentene) are preferable, and methylpentene is most preferable.
  • this LLDPE preferably contains ⁇ -olefin as a comonomer in an amount of 10 mol % or less and has a number average molecular weight of 10000 or more measured by GPC calibrated with polystyrene. That is, when the content of the ⁇ -olefin as a comonomer is large or when the number average molecular weight is small and the low molecular weight component is contained in a large amount, when used as a pouch, the oil resistance and the flavor property imparted to the contents deteriorate.
  • the composition of the film is preferably designed so that the amount of LLDPE (B) described above in the CPP film (corresponding to the amount of LLDPE in the heat-sealing resin layer 5 ) is 20% by mass or less. That is, if the content of LLDPE is excessive, the blocking resistance and heat resistance of the film may be impaired.
  • a known additive may be blended in an amount within a range that does not impair recyclability.
  • the CPP film including the impact PP component described above is produced by dry-blending components and feeding them to an extruder to melt-knead them, melt-extruding the blend into a film shape from a T-die, and bringing the extruded film-shaped melt into contact with a cooling roll to solidify the melt and a solidified film is wound.
  • the thickness of such a CPP film is not particularly limited but typically is in a range from 20 to 100 ⁇ m and, in particular, preferably from 50 to 80 ⁇ m in consideration of rigidity, openability, and the like.
  • a printed layer or a transparent protective layer may be layered on the outer surface side of the barrier film 1 .
  • thermoplastic resin film 1 a serving as a base of the inorganic coating 1 b
  • a stretched film layer containing at least one selected from an olefin-based resin, a polyamide-based resin, and an ethylene-vinyl alcohol copolymer is preferably provided as a strength reinforcing layer on the outer surface of the stretched film (thermoplastic resin film 1 a ) or between the inorganic coating 1 b and the adhesive layer 3 .
  • such a strength reinforcing layer is different from the thermoplastic resin film 1 a (a film serving as a base of the inorganic coating 1 b ) in the barrier film 1 , and serves to mitigate the loss of orientation due to heat treatment such as heat sealing treatment and to effectively suppress a decrease in strength.
  • Such a strength reinforcing layer is a stretched molding of a blend or a layered product of an olefin-based resin and a reinforcing resin having a melting point higher than that of the olefin-based resin.
  • a stretched film of a blend of an olefin-based resin and a polyamide-based resin or an ethylene-vinyl alcohol copolymer is preferable, and the mass ratio of the olefin-based resin:the reinforcing resin is usually in the range of about from 50:50 to 90:10. That is, when the amount of the reinforcing resin is excessively large, the strength reinforcing effect is excellent but the recyclability is low, and when the amount of the reinforcing resin is small, the strength reinforcing effect of this layer is impaired.
  • the strength reinforcing layer may have a layered structure in which a layer of an olefin-based resin and a layer of a reinforcing resin are layered.
  • the thickness ratio of the olefin-based resin layer: the reinforcing resin layer is usually in a range of about from 1/1 to 3/1. That is, when the thickness of the reinforcing resin is excessively large, the recyclability of the packaging bag is largely lost, and when the amount of the reinforcing resin is small, the amount of oriented crystals present in the sealing portion is small, and there is a possibility that the improvement of the bag drop strength is insufficient.
  • the above-described olefin-based resins used for forming the strength reinforcing layer are preferably the same olefin-based resins as those used for forming the above-described thermoplastic resin film 1 a , and polypropylene is the most suitable.
  • the polyamide to be blended with the above-described olefin-based resin is not particularly limited and may be exemplified by various ones, but in general, nylon 6, nylon 6,6, nylon 11, nylon 12, nylon 13, nylon 6/nylon 6,6 copolymer, aromatic nylon (for example, polymetaxylylene adipamide) and the like are preferably used.
  • the above-described strength reinforcing layer may be formed by co-extruding and stretch-molding a blend or by multilayer-extruding and stretch-molding a blend. Stretching may be performed in one or two axial directions.
  • this strength reinforcing layer is not particularly limited, and may be appropriately set to the thickness of the thermoplastic resin film 1 a which is set according to the volume and the like of the intended pouch.
  • the thickness is preferably 5 ⁇ m or more, and in particular preferably in the range of about from 5 to 30 ⁇ m.
  • thermoplastic resin film 1 a and strength reinforcing layer may all have molecular weights sufficient to form a film.
  • the adhesive layer 3 is also provided between the strength reinforcing layer and the heat-sealing resin layer 5 . That is, the layer structure of the layered body for packaging at this time is barrier film/adhesive layer/strength reinforcing layer/adhesive layer/heat-sealing resin layer.
  • the above-described layered body for packaging of the present invention is used as a pouch (bag-like container) after being formed into a bag by bonding by heat sealing with the heat-sealing resin layer.
  • Bag making is performed by known means. For example, an empty pouch is produced by three-side sealing using two layered bodies, contents are filled from the opening portion, and finally the opening portion is closed by heat sealing.
  • the pouch thus produced from the layered body for packaging of the present invention and filled with contents has excellent oxygen barrier properties and is also excellent in terms of heat resistance and impact resistance, and even when subjected to sterilization treatment (retort treatment) with heated steam at 100 to 130° C., a decrease in oxygen barrier properties is effectively avoided and excellent oxygen barrier properties are maintained.
  • sterilization treatment retort treatment
  • Such pouches are therefore particularly well suited for containing foodstuffs.
  • the olefin-based resin is 80% by mass or more.
  • LLDPE Linear Low-Density Polyethylene
  • Barrier oriented polypropylene film- 1 (barrier film- 1 );
  • Barrier oriented polypropylene film- 2 (barrier film- 2 )
  • OPP film Oriented polypropylene film
  • Epoxy-based adhesive Maxive available from Mitsubishi Gas Chemical Company, Inc.
  • Urethane-based adhesive A available from Toyo Morton Co., Ltd.
  • Urethane-based adhesive B PASLIM available from DIC Corporation
  • the layer configuration, lamination, bag making and retort of the laminate film are as follows.
  • barrier film barrier oriented polypropylene
  • adjuvant/sealant film a three-layer structure laminated in a configuration of another film (oriented polypropylene)/barrier film/sealant film were produced.
  • Lamination was performed by a dry lamination method to obtain a layered body.
  • the adhesive (coating liquid) was applied using a bar coater.
  • the coating amount was about 4 g/m 2 in terms of solid content.
  • the inorganic coating surface was layered so as to face the sealant side.
  • the surface other than the inorganic coating surface was subjected to corona discharge treatment to make the surface hydrophilic.
  • the lamination was performed so that the inorganic coating surface faced the other film side. After the lamination, curing was performed at for 4 days.
  • the laminated film (layered body) was cut into two pieces of 140 mm ⁇ 180 mm, filled with 200 g of water, and formed into a bag.
  • An Impulse Sealer available from Fuji Impulse Co., Ltd. was used for sealing.
  • the coating liquid of the adhesive was applied to the vapor-deposited surface of the barrier film using a bar coater.
  • the coating amount was about 4 g/m 2 in terms of solid content.
  • OX-TRAN2/22 available from MOCON, Inc. was used for measurement under the condition of 40° C. 90% RH.
  • the coating film elastic modulus of the epoxy-based adhesive (Maxive) was measured.
  • a coating liquid of an epoxy-based adhesive was applied to the vapor-deposited surface of the barrier stretched polypropylene film- 1 (coating amount in terms of solid: about 4 g/m 2 ), and a sealant film (CPP film- 1 ) was laminated thereon by a dry lamination method to obtain a layered body having a two-layer structure.
  • the layered body was used to make a pouch (filled with 200 g of water)(filled with 200 g of water), and then a retort treatment was performed. At this time, the oxygen permeability before and after the retort treatment was measured.
  • Example 2 Using the same epoxy-based adhesive as in Example 1, a layered body having a three-layer structure formed of OPP film/adhesive/barrier film- 1 /adhesive/CPP film- 1 was produced.
  • This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • Example 2 Using the same epoxy-based adhesive as in Example 1, a layered body having a three-layer structure formed of OPP film/adhesive/barrier film- 1 /adhesive/CPP film- 2 was produced.
  • This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • Example 2 Using the same epoxy-based adhesive as in Example 1, a layered body having a three-layer structure formed of OPP film/adhesive/barrier film- 1 /adhesive/CPP film- 3 was produced.
  • This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • Example 2 Using the same epoxy-based adhesive as in Example 1, a layered body having a three-layer structure formed of OPP film/adhesive/barrier film- 1 /adhesive/LLDPE film was produced. This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • Example 2 Using the same epoxy-based adhesive as in Example 1, a layered body having a two-layer structure formed of barrier film- 2 /adhesive/CPP film- 1 was produced. This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • the coating film elastic modulus obtained with the coating liquid a of the urethane-based adhesive A was measured.
  • Example 2 In the same manner as in Example 1 except that the above-described adhesive was used, a layered body having a two-layer structure formed of barrier film- 1 /adhesive/CPP film- 1 was produced, the layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability before and after the retort treatment was measured.
  • the coating film elastic modulus obtained with the urethane-based adhesive B was measured.
  • Example 2 In the same manner as in Example 1 except that the above-described adhesive was used, a layered body having a two-layer structure formed of barrier film- 1 /adhesive/CPP film- 1 was produced, the layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability before and after the retort treatment was measured.
  • the coating film elastic modulus obtained with the coating liquid b of the urethane-based adhesive A was measured.
  • Example 2 In the same manner as in Example 1 except that the above-described adhesive was used, a layered body having a sealant film structure of a layer configuration formed of barrier film- 1 /adhesive/CPP film- 1 was produced, the layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability before and after the retort treatment was measured.
  • a layered body having a three-layer structure formed of OPP film/adhesive/barrier film- 1 /adhesive/CPP film- 1 was produced. This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • a layered body having a three-layer structure formed of OPP film/adhesive/barrier film- 1 /adhesive/LLDPE film was produced. This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.
  • a layered body having a two-layer structure composed of barrier film- 2 /adhesive/CPP film- 1 was produced. This layered body was used to make a pouch, a retort treatment was performed, and the oxygen permeability after the retort treatment was measured.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
US18/025,516 2020-09-11 2021-09-10 Layered body for packaging Pending US20240010404A1 (en)

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EP4212334A4 (en) 2024-08-28

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